EP0239674B1 - Galvanic element - Google Patents

Galvanic element Download PDF

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Publication number
EP0239674B1
EP0239674B1 EP86116969A EP86116969A EP0239674B1 EP 0239674 B1 EP0239674 B1 EP 0239674B1 EP 86116969 A EP86116969 A EP 86116969A EP 86116969 A EP86116969 A EP 86116969A EP 0239674 B1 EP0239674 B1 EP 0239674B1
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EP
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Prior art keywords
zinc
alloy
anode
cup
cups
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EP86116969A
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German (de)
French (fr)
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EP0239674A1 (en
Inventor
Gerd Jung
Klaus Rüggeberg
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VARTA Batterie AG
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VARTA Batterie AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes

Definitions

  • the invention relates to a galvanic primary element with a flat, hollow cylindrical or cup-shaped zinc anode, a cathode depolarizer and a separator formed from a gel electrolyte or a gel / electrolyte-coated carrier material.
  • the zinc anode is separated from the cathode introduced as a compact or also directly pressed in by means of a container lining made of a gel electrolyte-coated carrier material or only with gel electrolyte.
  • Zinc chloride to which some ammonium chloride can optionally be added, is preferably used as the actual conductive salt. However, it can also be used as an electrolyte in accordance with the classic Leclanche cell ammonia solution. Some of the anode zinc is always dissolved by this, so that this electrolyte inevitably also contains some zinc chloride.
  • Drying elements of this type tend to self-discharge during storage, which can only be partially suppressed by constructive measures. Rather, the quality of the materials used and the surface finish of the zinc cup influence the storage behavior of the battery. These properties affect all processes in the reaction zone that are caused by the tendency of zinc to dissolve. They result from the low deposition overvoltage of the zinc in acid solution.
  • zinc corrosion can be inhibited both on the zinc itself by adding alloys and by adding substances with an inhibitory effect.
  • DE-PS 1 086 309 has therefore already proposed the addition of indium metal to the fine zinc on which the solution electrode is based or the addition of an indium salt to the electrolyte.
  • DE-PS 2 320 555 discloses the use of polyethylene glycol monolauryl ether as an organic corrosion inhibitor which is distinguished by good solubility in electrolytes.
  • Electrodes cups So-called fine zinc with a zinc content of 99.95 to 99.995 is used for the electrode cups, which is usually alloyed with lead and cadmium.
  • lead promotes mechanical workability, especially the rollability of zinc, and increases its corrosion resistance.
  • Cadmium which forms a solid solution with zinc, improves its hardness.
  • the object of the invention is to make available a primary element which is environmentally friendly and with this property without restriction according to the conventional methods of battery technology can be realized.
  • the Pb content is preferably 0.1 to 0.3%.
  • the alloy composition according to the invention thus differs from those previously used used cup alloys essentially by eliminating the environmentally harmful Cd component without replacement. It could be demonstrated in the corrosion test that anodes according to the invention behave similarly resistant even without the additional inhibition in comparison with anodes which are also not inhibited and which consist of fine zinc or of a Zn-0.25 Pb-0.06 Cd alloy.
  • the organic inhibitor polyethylene glycol monolauryl ether is present in an amount of 0.001 to 2% by weight, preferably 0.01 to 0.2% by weight, based on the battery weight. It is best placed in the electrolyte before it is gelled and, if necessary, can be dissolved beforehand with a little alcohol.
  • the zinc cups are exposed to mechanical loads during production and cell assembly, which require a minimum of dimensional stability.
  • alloying lead and cadmium as fine grain formers to fine zinc had previously achieved a considerable improvement in the cup stiffness.
  • unalloyed fine zinc is very easily deformable due to the coarse grain structure.
  • Anode sections according to the invention were found to withstand the loads in the comparative deformation test, as were anode sections made of conventional, Cd-containing alloy (cf. FIG. 1 and below).
  • the primary element according to the invention is not inferior in capacity behavior to other comparable dry elements with conventional anode cups and without inhibition. This resulted in a test that was carried out on dry elements of the Leclanche type based on the Zn / ZnC1 2 / MnO 2 system with the cell size IEC R 20 and on atmospheric oxygen elements of the size IEC AR 40.
  • dry elements of the Leclanche type based on the Zn / ZnC1 2 / MnO 2 system with the cell size IEC R 20 and on atmospheric oxygen elements of the size IEC AR 40.
  • natural, electrolyte or chemical brown stones can be used alone or in combination as brown stone types.
  • the anode consisted of a zinc cup with the alloy composition Zn - 0.25 Pb, the cathode made of manganese dioxide, conductive carbon black, zinc oxide, zinc chloride and water, the separator from gel-electrolyte-coated special paper, which at the same time the inventive Inhibitor contained.
  • the anode was a zinc material made of Zn-0.25 Pb
  • the cathode was a mixture of activated carbon, conductive carbon black, ammonium chloride and water
  • the separator was again made using the inhibitor-containing gel electrolyte.
  • the ordinate is the degree of deformation s in%, which the anode section suffers in the axial direction as a function of the specified composition under a load of 5 kg.
  • cups according to the invention have proven to be comparable.
  • a deformation minimum at e 12%, which would be achievable by means of 0.06% alloyed Cd, does not justify the presence of the undesired metal in this case, because the Cd-free cup alloy already meets the strength requirements placed on it.
  • FIGS. 2 and 3 generally show that the environmentally friendly measures according to the invention at least do not have to accept any significant loss of capacity of the primary element.
  • the essence of the invention can be summarized in that it is possible to produce primary elements in the usual quality with regard to storage behavior and electrical performance, without adding cadmium to the fine zinc intended for the production of the anode cups. Any trace presence of cadmium in the cup alloy is less than 10 mg / kg battery within the scope of the external admixtures approved for fine zinc according to DIN 1706. Such a cadmium-free primary element and, thanks to the use of an organic inhibitor, also mercury-free, greatly complies with the efforts of environmental science.

Description

Die Erfindung betrifft ein galvanisches Primärelement mit einer flachen, hohlzylindrischen oder becherförmigen Zinkanode, einem Kathodendepolarisator und einem aus Gel-Elektrolyt oder Gel-/Elektrolyt-beschichtetem Trägermaterial gebildeten Separator.The invention relates to a galvanic primary element with a flat, hollow cylindrical or cup-shaped zinc anode, a cathode depolarizer and a separator formed from a gel electrolyte or a gel / electrolyte-coated carrier material.

Diesem Gattungsbegriff lassen sich allgemein Primärelemente zuordnen, bei denen ungeachtet sonstiger Varianten hinsichtlich der Zellenkonstruktion ein Zinkbehälter gleichzeitig das Zellengehäuse und die negative Elektrode bildet. Die Herstellung dieser Zinkanode erfolgte früher überwiegend durch Tiefziehen von Zinkband, heute bevorzugt durch Fließpressen von gestanzten oder gegossenen Kalotten.Primary elements can generally be assigned to this generic term, in which, regardless of other variants with regard to the cell construction, a zinc container simultaneously forms the cell housing and the negative electrode. In the past, this zinc anode was mainly produced by deep-drawing zinc strip, today it is preferred to extrude stamped or cast domes.

Nach der Formgebung liegt somit eine Anode vor, deren Wanddicke sowohl die mechanische Stabilität als auch den Kapazitätsüberschuß bestimmt. Gegen die als Preßling eingebrachte oder auch direkt eingepreßte Kathode ist die Zinkanode mittels einer Behälterauskleidung aus Gel-Elektrolyt-beschichtetem Trägermaterial oder nur mit Gel-Elektrolyt separiert. Als eigentliches Leitsalz dient vorzugsweise Zinkchlorid, dem ggf. etwas Ammoniumchlorid beigefügt sein kann. Es ist aber auch entsprechend der klassischen Leclanche-Zelle Salmiaklösung als Elektrolyt verwendbar. Von dieser wird stets etwas Anodenzink aufgelöst, so daß dieser Elektrolyt zwangsläufig auch etwas Zinkchlorid enthält.After shaping, there is thus an anode, the wall thickness of which determines both the mechanical stability and the excess capacity. The zinc anode is separated from the cathode introduced as a compact or also directly pressed in by means of a container lining made of a gel electrolyte-coated carrier material or only with gel electrolyte. Zinc chloride, to which some ammonium chloride can optionally be added, is preferably used as the actual conductive salt. However, it can also be used as an electrolyte in accordance with the classic Leclanche cell ammonia solution. Some of the anode zinc is always dissolved by this, so that this electrolyte inevitably also contains some zinc chloride.

Trockenelemente dieser Art neigen während der Lagerung zur Selbstentladung, die nur zum Teil durch konstruktive Maßnahmen unterdrückt werden kann. Vielmehr beeinflußt die Qualität der verwendeten Materialien wie auch die Oberflächenbeschaffenheit des Zinkbechers das Lagerverhalten der Batterie. Diese Eigenschaften wirken sich auf alle Vorgänge in der Reaktionszone, die durch die Lösungsneigung des Zinks bedingt sind, aus. Sie resultieren aus der niedrigen Abscheidungsüberspannung des Zinks in saurer Lösung.Drying elements of this type tend to self-discharge during storage, which can only be partially suppressed by constructive measures. Rather, the quality of the materials used and the surface finish of the zinc cup influence the storage behavior of the battery. These properties affect all processes in the reaction zone that are caused by the tendency of zinc to dissolve. They result from the low deposition overvoltage of the zinc in acid solution.

Dabei kann eine Inhibierung der Zinkkorrosion sowohl am Zink selbst durch Legierungszusätze als auch durch Zufügen inhibierend wirkender Substanzen erzielt werden.In this case, zinc corrosion can be inhibited both on the zinc itself by adding alloys and by adding substances with an inhibitory effect.

Das an sich übliche, zum Schutz des Zinks angewandte Verfahren der Amalgamierung ist bei sauren Elektrolytlösungen, selbst bei Verwendung von sehr reinem Zink, welches dem Säureangriff eher als unreines Zink widersteht, oft nicht ausreichend, da die Schutzwirkung des Quecksilbers auf die Dauer eine Lochfraßkorrosion nicht verhindert. In der DE-PS 1 086 309 wurde daher bereits die Zulegierung von Indiummetell zu dem der Lösungselektrode zugrundeliegenden Feinzink oder der Zusatz eines Indiumsalzes zum Elektrolyten vorgeschlagen. Die DE-PS 2 320 555 offenbart die Verwendung von Polyäthylenglycolmonolauryläther als einen organischen Korrosionsinhibitor, der sich durch gute Elektrolytlöslichkeit auszeichnet.The usual amalgamation method used to protect the zinc is often not sufficient with acidic electrolyte solutions, even when using very pure zinc, which is more resistant to acid attack than impure zinc, since the protective effect of mercury is not pitting corrosion in the long run prevented. DE-PS 1 086 309 has therefore already proposed the addition of indium metal to the fine zinc on which the solution electrode is based or the addition of an indium salt to the electrolyte. DE-PS 2 320 555 discloses the use of polyethylene glycol monolauryl ether as an organic corrosion inhibitor which is distinguished by good solubility in electrolytes.

Für die Elektrodenbecher kommt sogenanntes Feinzink mit einem Zinkgehalt von 99,95 bis 99,995 zur Verarbeitung, dem in aller Regel Blei und Cadmium zulegiert ist. Von diesen fördert Blei die mechanische Verarbeitbarkeit, insbesondere die Walzbarkeit des Zinks, und erhöht seine Korrosionsfestigkeit. Durch Cadmium, das mit Zink eine feste Lösung bildet, wird dessen Härte verbessert.So-called fine zinc with a zinc content of 99.95 to 99.995 is used for the electrode cups, which is usually alloyed with lead and cadmium. Of these, lead promotes mechanical workability, especially the rollability of zinc, and increases its corrosion resistance. Cadmium, which forms a solid solution with zinc, improves its hardness.

R. Huber ("Trockenbatterien", VARTA Fachbuchreihe Band 2, 2. Aufl. 1968, Seite 24, VDI-Verlag Düsseldorf) gibt die Zusammensetzung geeigneter Zinklegierungen mit 0,06 - 0,1% Pb und 0,05 - 0,07% Cd für gezogene Becher, mit 0,1 - 1% Pb und 0 - 0,06% Cd für gespritzte Becher an. Aus N.C. Cahoon und G.W. Heise (The Primary Battery, Vol. 2 1976, John Wiley and Sons, New York, Seite 57) kann man entnehmen, daß für das Fließpressen von Zinkbechern eine Legierung mit ca. 0,1% Pb und 0,05% Cd am besten geeignet ist, daß diese Legierung ein relativ feinkörniges Gefüge besitzt und im übrigen der für das Tiefziehen von Bechern verwendeten Legierungszusammensetzung nahekommt. G.W. Vinal (Primary Batteries, John Wiley and Sons, New York, Seite 77) nennt sogar je 0,3% Pb und Cd als übliche Zusätze zum Zink, welches für Trockenelementebecher eingesetzt wird. Eine Einschränkung soll nur bei gezogenen Bechern insoweit gelten, als der Cd-Gehalt dort auf 0,1% und darunter herabgesetzt ist, da höhere Cd-Gehalte das Tiefziehen erschweren.R. Huber ("Trockenbatterien", VARTA specialist book series volume 2, 2nd edition 1968, page 24, VDI-Verlag Düsseldorf) gives the composition of suitable zinc alloys with 0.06 - 0.1% Pb and 0.05 - 0.07 % Cd for drawn cups, with 0.1 - 1% Pb and 0 - 0.06% Cd for molded cups. From N.C. Cahoon and G.W. Heise (The Primary Battery, Vol. 2 1976, John Wiley and Sons, New York, page 57) shows that an alloy with approximately 0.1% Pb and 0.05% Cd is best for extruding zinc cups it is suitable that this alloy has a relatively fine-grained structure and, moreover, approximates the alloy composition used for deep-drawing cups. G.W. Vinal (Primary Batteries, John Wiley and Sons, New York, page 77) even mentions 0.3% Pb and Cd as common additives to the zinc, which is used for dry element cups. A restriction should only apply to drawn cups insofar as the Cd content there is reduced to 0.1% and below, since higher Cd contents make deep drawing difficult.

Angesichts dieses Standes der Becherfertigung, vorzugsweise im Fließpreßverfahren als Massenartikel, und auf der Basis einer weitgehend festgeschriebenen Zusammensetzung des Zinkmaterials liegt der Erfindung die Aufgabe zugrunde, ein Primärelement verfügbar zu machen, welches umweltfreundlich ist und mit dieser Eigenschaft ohne Einschränkung nach den konventionellen Verfahren der Batterietechnik realisiert werden kann.In view of this state of the cup production, preferably in the extrusion process as a mass article, and on the basis of a largely fixed composition of the zinc material, the object of the invention is to make available a primary element which is environmentally friendly and with this property without restriction according to the conventional methods of battery technology can be realized.

Die Aufgabe wird erfindungsgemäß mit den im kennzeichnenden Teil des Anspruchs 1 angegebenen Maßnahmen gelöst.The object is achieved with the measures specified in the characterizing part of claim 1.

Danach hat sich gezeigt, daß ein Legierungsmaterial aus den alleinigen Komponenten Zink und Blei allen Anforderungen an den Anodenbecher in zumindest dem gleichen Umfange gerecht wird, wie die sonst verwendete Zink/Blei/Cadmium-Legierung, wenn in Verbindung mit der Zn-Pb-Legierung ohne zulegiertes Cadmium ein Polyäthylenglycolmonolauryläther enthaltender Elektrolyt eingesetzt wird. Insbesondere wurde gefunden, daß die Becherkorrosion mit den erfindungsgemäßen Maßnahmen erheblich reduziert werden kann. So ergab ein in 3n HCI bei 20°C durchgeführt Korrosionstest von 40 min. Dauer einen Gewichtsverlust von 418 mg für reines Zink und von 180 mg für eine Legierung Zn - o,25 Pb - 0,06 Cd, dagegen von nur 55 mg für Zn - 0,25 Pb und 63 mg für Zn - 0,45 Pb. Die Zahlenangaben Zn, Pb und Cd sind Prozente; in allen Fällen waren dir Zinkbecher durch den erfindungsgemäßen Glycoläther inhibiert.It has subsequently been shown that an alloy material consisting of the sole components zinc and lead meets all the requirements for the anode cup in at least the same extent as the zinc / lead / cadmium alloy otherwise used when combined with the Zn-Pb alloy an electrolyte containing polyethylene glycol monolauryl ether is used without added cadmium. In particular, it has been found that cup corrosion can be considerably reduced with the measures according to the invention. A corrosion test of 40 min, carried out in 3N HCl at 20 ° C, resulted. Duration a weight loss of 418 mg for pure zinc and 180 mg for an alloy Zn - o, 25 Pb - 0.06 Cd, whereas only 55 mg for Zn - 0.25 Pb and 63 mg for Zn - 0.45 Pb . The numbers Zn, Pb and Cd are percentages; in all cases zinc cups were inhibited by the glycol ether according to the invention.

Für die cadmiumfreie Becherlegierung hat sich erfindungsgemäß ein Gehalt von 0,1 bis 0,6% Pb im restlichen Feinzink, dessen Reinheit mindestens 99,95 betragen soll, als günstig erwiesen. Vorzugsweise liegt der Pb-Gehalt bei 0,1 bis 0,3%.For the cadmium-free cup alloy, a content of 0.1 to 0.6% Pb in the remaining fine zinc, the purity of which should be at least 99.95, has proven to be favorable. The Pb content is preferably 0.1 to 0.3%.

Die erfindungsgemäße Legierungszusammensetzung unterscheidet sich damit von den bisher verwendeten Becherlegierungen im wesentlichen dadurch, daß die umweltschädliche Cd-Komponente ersatzlos entfallen ist. Dabei konnte im Korrosionstest nachgewiesen werden, daß sich erfindungsgemäße Anoden auch ohne die zusätzliche Inhibierung im Vergleich zu ebenfalls nicht inhibierten aus Feinzink bzw. aus einer Zn- 0,25 Pb - 0,06 Cd-Legierung bestehenden Anoden ähnlich resistent verhalten.The alloy composition according to the invention thus differs from those previously used used cup alloys essentially by eliminating the environmentally harmful Cd component without replacement. It could be demonstrated in the corrosion test that anodes according to the invention behave similarly resistant even without the additional inhibition in comparison with anodes which are also not inhibited and which consist of fine zinc or of a Zn-0.25 Pb-0.06 Cd alloy.

Die auch hier mit zunehmendem Bleigehalt steigende Inhibierung läßt sich mit der Verfeinerung des Zinkkorngefüges und Anhebung der Überspannung erklären. Sehr hohe Bleianteile (> 0,6%) sind aber wegen der dann verstärkt auftretenden "pitting corrosion" nicht ratsam.The increase in inhibition, which also increases with the lead content, can be explained by the refinement of the zinc grain structure and an increase in the overvoltage. Very high proportions of lead (> 0.6%) are not advisable because of the increasing pitting corrosion.

Der organische Inhibitor Polyäthylenglycolmonolauryläther ist erfindungsgemäß in einer Menge von 0,001 bis 2 Gew.%, vorzugsweise 0,01 bis 0,2 Gew.%, bezogen auf das Batteriegewicht, vorhanden. Er wird am besten in den Elektrolyten vor dessen Gelifizierung eingebracht und kann, falls nötig, vorher mit wenig Alkohol in Lösung gebracht werden.According to the invention, the organic inhibitor polyethylene glycol monolauryl ether is present in an amount of 0.001 to 2% by weight, preferably 0.01 to 0.2% by weight, based on the battery weight. It is best placed in the electrolyte before it is gelled and, if necessary, can be dissolved beforehand with a little alcohol.

Eine weitere, vom Batterieherstellungsprozeß diktierte Forderung, wird von der erfindungsgemäßen Legierung einwandfrei erfüllt: Die Zinkbecher sind während der Fertigung und der Zellenmontage mechanischen Belastungen ausgesetzt, die ein Mindestmaß an Formstabilität verlangen. Um den notwendigen Widerstand gegen Deformationen zu erreichen, hatte man bisher durch Zulegieren von Blei und Cadmium als Feinkornbildner zum Feinzink eine beträchtliche Verbesserung der Bechersteifigkeit erzielt. Unlegiertes Feinzink ist demgegenüber wegen des groben Korngefüges sehr leicht verformbar. Erfindungsgemäße Anodenabschnitte zeigten sich beim vergleichenden Verformungstest den Belastungen ebenso gewachsen wie Anodenabschnitte aus konventioneller, Cd-haltiger Legierung (vgl. hierzu Fig. 1 und weiter unten).Another requirement dictated by the battery manufacturing process is perfectly fulfilled by the alloy according to the invention: the zinc cups are exposed to mechanical loads during production and cell assembly, which require a minimum of dimensional stability. In order to achieve the necessary resistance to deformation, alloying lead and cadmium as fine grain formers to fine zinc had previously achieved a considerable improvement in the cup stiffness. In contrast, unalloyed fine zinc is very easily deformable due to the coarse grain structure. Anode sections according to the invention were found to withstand the loads in the comparative deformation test, as were anode sections made of conventional, Cd-containing alloy (cf. FIG. 1 and below).

Das Primärelement gemäß der Erfindung steht schließlich auch im Kapazitätsverhalten anderen vergleichbaren Trockenelementen mit konventionellen Anodenbechem und ohne Inhibierung nicht nach. Dies ergab ein Test, der an Trockenelementen vom Leclanche-Typ auf der Grundlage des Systems Zn/ZnC12/MnO2 mit der Zellengröße IEC R 20 sowie an Luftsauerstoffelementen der Größe IEC AR 40 durchgeführt wurde. Als Braunsteintypen können alternativ Natur-, Elektrolyt- oder chemische Braunsteine allein oder in Kombination verwendet werden.Finally, the primary element according to the invention is not inferior in capacity behavior to other comparable dry elements with conventional anode cups and without inhibition. This resulted in a test that was carried out on dry elements of the Leclanche type based on the Zn / ZnC1 2 / MnO 2 system with the cell size IEC R 20 and on atmospheric oxygen elements of the size IEC AR 40. Alternatively, natural, electrolyte or chemical brown stones can be used alone or in combination as brown stone types.

Im einzelnen bestand bei den erstgenannten Zellen die Anode aus einem Zinkbecher mit der Legierungszusammensetzung Zn - 0,25 Pb, die Kathode aus Braunstein, leitfähigem Ruß, Zinkoxid, Zinkchlorid und Wasser, der Separator aus Gel-Elektrolyt-beschichtetem Spezialpapier, das zugleich den erfindungsgemäßen Inhibitor enthielt. Bei den Luftsauerstoffelementen war die Anode ein Zinkmaterial aus Zn - 0,25 Pb, die Kathode ein Gemisch aus Aktivkohle, leitfähigem Ruß, Ammoniumchlorid und Wasser, und der Separator wiederum unter Verwendung des inhibitorhaltigen Gel-Elektrolyt hergestellt.Specifically, the anode consisted of a zinc cup with the alloy composition Zn - 0.25 Pb, the cathode made of manganese dioxide, conductive carbon black, zinc oxide, zinc chloride and water, the separator from gel-electrolyte-coated special paper, which at the same time the inventive Inhibitor contained. For the atmospheric oxygen elements, the anode was a zinc material made of Zn-0.25 Pb, the cathode was a mixture of activated carbon, conductive carbon black, ammonium chloride and water, and the separator was again made using the inhibitor-containing gel electrolyte.

Die Befunde zur mechanischen Festigkeit der Anodenbecher und zum Kapazitätsverhalten der erfindungsgemäßen Primärelemente werden durch die nachstehenden Abbildungen verdeutlicht.

  • Figur 1 zeigt Verformungsgrade von Zinkbechern in Abhängigkeit von Legierungszusätzen.
  • Figur 2 zeigt Kapazitäten erfindungsgemäßer Primärelemente vom Leclanche-Typ im Vergleich zu konventionellen Primärelementen unter verschiede- . nen Bedingungen der Lagerung und Stromentnahme.
  • Figur 3 zeigt einen Kapazitätsvergleich ähnlich wie Figur 2 für Luftsauerstoffelemente.
The results of the mechanical strength of the anode cups and the capacity behavior of the primary elements according to the invention are illustrated by the figures below.
  • Figure 1 shows degrees of deformation of zinc cups as a function of alloy additives.
  • FIG. 2 shows capacities of primary elements of the Leclanche type according to the invention in comparison to conventional primary elements under different. conditions of storage and power consumption.
  • Figure 3 shows a capacity comparison similar to Figure 2 for atmospheric oxygen elements.

In der Graphik nach Figur 1 ist als Ordinate der Verformungsgrad s in % aufgetragen, den der Anodenabschnitt in Abhängigkeit von der angegebenen Zusammensetzung bei einer Belastung mit 5 kg in Axialrichtung erleidet. Gegenüber einem konventionellen Becher aus Cd-haltiger Legierung erweisen sich erfindungsgemäße Becher als vergleichbar. Ein bei e= 12% liegendes Verformungsminimum, welches mittels 0,06% zulegiertem Cd erzielbar wäre, rechtfertigt in diesem Fall nicht die Anwesenheit des unerwünschten Metalls, weil die Cd-freie Becherlegierung bereits den an sie gestellten Festigkeitsanprüchen genügt.In the graph of FIG. 1, the ordinate is the degree of deformation s in%, which the anode section suffers in the axial direction as a function of the specified composition under a load of 5 kg. Compared to a conventional cup made of Cd-containing alloy, cups according to the invention have proven to be comparable. A deformation minimum at e = 12%, which would be achievable by means of 0.06% alloyed Cd, does not justify the presence of the undesired metal in this case, because the Cd-free cup alloy already meets the strength requirements placed on it.

Aus den Balkendiagrammen der Figuren 2 und 3 geht allgemein hervor, daß mit den erfindungsgemä- Ben umweltfreundlichen Maßnahmen zumindest keine nennenswerten Kapazitätseinbußen des Primärelements in Kauf genommen werden müssen.The bar diagrams in FIGS. 2 and 3 generally show that the environmentally friendly measures according to the invention at least do not have to accept any significant loss of capacity of the primary element.

Die jeweils auf die Ordinate aufgetragene Kapazität Q (Ah) bezieht sich auf verschiedene Entladebedingungen, nämlich in Figur 2 auf

  • 1) Konstantstromentladung über 5 Ohm
  • 2) Intermittierende Entladung von 2 Std. pro Tag über 5 Ohm
  • 3) Entladung nach LIFT (Light Industrial Flashlight-Test) über 2,2 Ohm
  • 4) Intermittierende Entladung von 4 h pro Tag über 20 Ohm
The capacitance Q (Ah) plotted on the ordinate relates to various discharge conditions, namely in FIG. 2
  • 1) Constant current discharge over 5 ohms
  • 2) Intermittent discharge of 2 hours per day over 5 ohms
  • 3) Discharge according to LIFT (Light Industrial Flashlight test) over 2.2 ohms
  • 4) Intermittent discharge of 4 h per day over 20 ohms

und in Figur 3 auf

  • 1) Konstantstromentladung über 5 Ohm
  • 2) Konstantstromentladung über 10 Ohm
  • 3) Konstantstromentladung über 25 Ohm
and in Figure 3
  • 1) Constant current discharge over 5 ohms
  • 2) Constant current discharge over 10 ohms
  • 3) Constant current discharge over 25 ohms

In den Figuren 2 und 3 bedeuten

  • 1: Konventionelles Element, ungelagert
  • 2: Konventionelles Element, 3 Monate bei 45°C gelagert
  • 3: Erfindungsgemäßes Element, ungelagert
  • 4: Erfindungsgemäßes Element, 3 Monate bei 45°C gelagert
In Figures 2 and 3 mean
  • 1: Conventional element, unsupported
  • 2: Conventional element, stored at 45 ° C for 3 months
  • 3: Element according to the invention, unsupported
  • 4: Element according to the invention, stored at 45 ° C. for 3 months

Der Kern der Erfindung läßt sich dahin zusammenfassen, daß es möglich ist, Primärelemente in gewohnter Qualität hinsichtlich Lagerverhalten und elektrischer Leistung herzustellen, ohne daß dem für die Herstellung der Anodenbecher bestimmten Feinzink in bislang üblicher Weise Cadmium zulegiert wird. Eine gegebenenfalls spurenweise Anwesenheit von Cadmium in der Becherlegierung liegt im Rahmen der für Feinzink nach DIN 1706 zugelassenen Fremdbeimengungen unter 10 mg/kg Batterie. Ein solches cadmiumfreies und durch den Einsatz eines organischen Inhibitors auch Hg-freies Primärelement, kommt den Bestrebungen des Umweltschultzes in hohem Maße entgegen.The essence of the invention can be summarized in that it is possible to produce primary elements in the usual quality with regard to storage behavior and electrical performance, without adding cadmium to the fine zinc intended for the production of the anode cups. Any trace presence of cadmium in the cup alloy is less than 10 mg / kg battery within the scope of the external admixtures approved for fine zinc according to DIN 1706. Such a cadmium-free primary element and, thanks to the use of an organic inhibitor, also mercury-free, greatly complies with the efforts of environmental science.

Claims (3)

1. Galvanic primary cell having a flat, hollow-cylindrical or cup-shaped zinc anode, a cathode depo- larizer and a separator formed from gel electrolyte or gevelectrolyte-coated support material, characterized in that the zinc comprises an alloy of 0.1 to 0.6% lead and the remainder is fine zinc having a purity of at least 99.95%, and in that polyethyleneglycol monolauryl ether is added as an inhibitor to the separator or mass.
2. Primary cell according to claim 1, characterized in that 0.1 to 0.3% lead is alloyed with the fine zinc.
3. Primary cell according to claims 1 and 2, characterized in that the amount of the inhibitor is 0.001 to 2% by weight, preferably 0.01 to 0.2% by weight, of the total weight of the primary cell.
EP86116969A 1986-02-22 1986-12-06 Galvanic element Expired - Lifetime EP0239674B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863605718 DE3605718A1 (en) 1986-02-22 1986-02-22 GALVANIC PRIME ELEMENT
DE3605718 1986-02-22

Publications (2)

Publication Number Publication Date
EP0239674A1 EP0239674A1 (en) 1987-10-07
EP0239674B1 true EP0239674B1 (en) 1990-03-07

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ID=6294695

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Application Number Title Priority Date Filing Date
EP86116969A Expired - Lifetime EP0239674B1 (en) 1986-02-22 1986-12-06 Galvanic element

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EP (1) EP0239674B1 (en)
DE (2) DE3605718A1 (en)
GR (1) GR3000368T3 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0352604A1 (en) * 1988-07-25 1990-01-31 Cipel Primary electrochemical generator with an alkaline electrolyte and a negative zinc electrode
US5270128A (en) * 1992-04-03 1993-12-14 Eveready Battery Company, Inc. Air assisted alkaline cell
US6284410B1 (en) 1997-08-01 2001-09-04 Duracell Inc. Zinc electrode particle form
US6472103B1 (en) 1997-08-01 2002-10-29 The Gillette Company Zinc-based electrode particle form
US6521378B2 (en) 1997-08-01 2003-02-18 Duracell Inc. Electrode having multi-modal distribution of zinc-based particles
US6602629B1 (en) * 2000-05-24 2003-08-05 Eveready Battery Company, Inc. Zero mercury air cell

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4118551A (en) * 1977-10-31 1978-10-03 Yardney Electric Corporation Mercury-free zinc electrode

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DE3605718A1 (en) 1987-08-27
EP0239674A1 (en) 1987-10-07
GR3000368T3 (en) 1991-06-07
DE3669422D1 (en) 1990-04-12

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